Micellization of copolymers via noncovalent interaction with TPPS and aggregation of TPPS

Aggregation of 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin (TPPS) was investigated in complex micelles composed of poly(ethylene glycol)- block -poly(4-vinylpyridine) (PEG- b -P4VP) and poly(2-(dimethylamino)ethyl methylacrylate)- b -poly( N -isopropylacrylamide) (PDMAEMA- b -PNIPAM) in aqueou...

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Bibliographic Details
Published in:Science China. Chemistry 2011-02, Vol.54 (2), p.343-350
Main Authors: Zhao, LiZhi, Xiang, Rui, Zhang, LiYan, Wu, ChengLin, Ma, RuJiang, An, YingLi, Shi, LinQi
Format: Article
Language:English
Subjects:
Aggregates
Aqueous solutions
Chemistry
Chemistry and Materials Science
Chemistry/Food Science
Copolymers
Micelles
Monomers
Polyelectrolytes
Polyethylene glycol
Polyisopropyl acrylamide
Polyvinyl pyridine
Porphyrins
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Summary:Aggregation of 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin (TPPS) was investigated in complex micelles composed of poly(ethylene glycol)- block -poly(4-vinylpyridine) (PEG- b -P4VP) and poly(2-(dimethylamino)ethyl methylacrylate)- b -poly( N -isopropylacrylamide) (PDMAEMA- b -PNIPAM) in aqueous solutions. The resultant complex micelles had a complex P4VP/PDMAEMA/TPPS core and a mixed PEG/PNIPAM shell. Different noncovalent interaction modes between the porphyrin and each copolymer accomplished a co-effect on the aggregation of TPPS. The formation of aggregates was pH-dependent. At pH 3.2–6.5, TPPS existed as a mixture of H-aggregates and monomers because of the aromatic-aromatic interaction with P4VP and electrostatic interaction with PDMAEMA. The monomers translated into J-aggregates, stabilized by electrostatic interaction with the both polyelectrolyte blocks, upon decreasing the pH to 1.6. The free-base monomer was the one and only form for the dye at pH 11.0 due to aromatic stacking with the pyridyl rings.
ISSN:1674-7291
1869-1870
DOI:10.1007/s11426-010-4202-x